JP6862971B2 - How to make polymer particles - Google Patents

Description

The present invention relates to a method for producing polymer particles. More specifically, the present invention relates to a method for producing polymer particles, which comprises forming an emulsifying solution containing droplets of a monoma solution using an emulsifying device having a flow path covered with a coating film containing an amphoteric polymer.

Conventionally, a suspension polymerization method is known as a method for synthesizing polymer particles having an average particle size of 100 μm or more. As a method for producing polymer particles having a large particle size and high monodispersity, a method is known in which an emulsion containing monoma droplets is formed using a microreactor emulsifier and the polymer particles are obtained in the obtained emulsion. (For example, Patent Document 1 and Patent Document 2).

JP-A-2010-142725 Japanese Unexamined Patent Publication No. 2013-163149

However, with the conventional method using a microreactor emulsifying device, it has been difficult to continuously and stably produce polymer particles having high monodispersity.

Therefore, one aspect of the present invention is to provide a method capable of continuously and stably producing polymer particles having high monodispersity.

One aspect of the present invention is to mix a polymer liquid containing a polymer with an aqueous liquid containing water in a flow path of an emulsifying device to obtain a droplet of the polymer liquid as a dispersed phase and the aqueous liquid as a continuous phase. Provided is a method for producing a polymer particle, which comprises a step of forming an emulsion containing the above, and a step of polymerizing the monoma in the emulsion to form a polymer particle containing the polymer of the monoma. .. In this method, the surface of the flow path is covered with a coating film containing an amphoteric polymer.

According to this method, polymer particles having a narrow particle size distribution, that is, highly monodisperse, can be continuously and stably produced. The coating film containing the amphoteric polymer suppresses the adsorption of the oily component, and the adsorbed oily component can be easily washed away.

According to the method according to the present invention, polymer particles having high monodispersity can be continuously and stably produced. In particular, an emulsified solution containing droplets of a monoma solution having a large particle size and high monodispersity can be stably formed by repeating it a plurality of times for a long period of time.

It is a schematic diagram which shows one Embodiment of an emulsification apparatus.

Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

One embodiment of the method for producing polymer particles is to disperse a monoma solution containing monoma into an aqueous solution containing water in a flow path of an emulsifying device, and use the monoma solution as a dispersion phase as a continuous phase with droplets of the monoma solution. It includes a step of forming an emulsion containing an aqueous solution and a step of polymerizing a monoma in the emulsion to form polymer particles containing a polymer of the monoma.
(Emulsification device)

As the emulsifying device, a general emulsifying device having a flow path for forming an emulsifying liquid can be used. The flow path can be, in particular, a micro flow path. The width of the microchannel may be, for example, 10 to 1000 μm. Commercially available products of emulsification equipment include, for example, microprocess server (manufactured by Hitachi, Ltd.), microchannel (manufactured by Synthetic Fiber Nozzle Mfg. Co., Ltd.), microchannel emulsifier (manufactured by EP Tech Co., Ltd.), SPG membrane emulsifier (SPG). (Made by Techno Co., Ltd.). A double-tube type microchannel is preferable because uniform droplet formation is easy and a large number of droplet formation channels can be provided in close contact with each other.

As a method of supplying the monoma solution and the aqueous solution to the emulsifying device, a usual method can be used. For example, a method of supplying with a pump and a method of supplying with water pressure using gravity can be mentioned. Examples of the pump include a syringe pump, a mono pump, a plunger pump, a diaphragm pump, a rotary pump, a tube pump, and a gear pump. As a method of supplying with water pressure using gravity, for example, the height difference between the microsphere manufacturing apparatus and the tank for supplying each of the monoma solution and the aqueous solution is adjusted, and the difference in water pressure between the monoma solution and the aqueous solution is used. There is a method of adjusting the flow rate balance of.

When a pulsating current occurs in each of the flow of the dispersed phase and the continuous phase, the monodispersity of the obtained polymer particles is affected. Therefore, it is preferable to take a method of suppressing the pulsating current as much as possible.

The emulsifying device can be made of metal, glass, or resin. The surface of the flow path may be formed of, for example, a resin such as polyester, a metal such as stainless steel, or glass. The surface of the flow path is preferably made of stainless steel or glass because it is hard to rust and is not easily corroded or deteriorated by the monoma. Hydroxyl groups may be present on the surface of the flow path, or silica may be vapor-deposited on the surface of the flow path. For example, a hydroxyl group is usually present on a surface formed of glass.

Examples of the resin constituting the surface of the flow path include polyamide typified by polyethylene, polypropylene, polystyrene, polyvinyl chloride and nylon, polyimide, polyurethane, urea resin, polylactic acid, polyvinyl alcohol, polyvinyl acetate and acrylic resin. Examples thereof include polysulfone, polycarbonate, ABS resin, AS resin, and silicone resin. Since the surface formed from these resins is usually hydrophobic, the coating film can be more firmly fixed by depositing silica on the surface.

Examples of the method for depositing silica on the surface include a vacuum vapor deposition method, a sputtering method, and a chemical vapor deposition method. For example, when silica is vapor-deposited on the surface of a flow path by a vacuum vapor deposition method, an emulsifying device having a flow path is placed in a vacuum vessel, degassed under heating, and then vapor of alkoxysilane such as tetramethoxysilane is vacuumed. Silane can be deposited on the surface of the flow path by introducing it into the container.

FIG. 1 is a schematic view showing an embodiment of an emulsification device. The emulsification device 1 shown in FIG. 1 has a first member 13 and a second member 14 facing each other, and an aqueous liquid 25 is filled between the first member 13 and the second member 14. A continuous phase supply path 15 is provided. A plurality of nozzles 12 for supplying the monoma liquid are mounted on the first member 13. The second member 14 forms a plurality of flow paths 10 having a tubular inner peripheral surface as a surface, and the nozzle 12 is arranged so that the tip of the nozzle 12 is located near the entrance of the flow path 10. ing. The surface 10S of the flow path 10 is covered with a coating film containing an amphoteric polymer.

While pouring the aqueous liquid 25 as a continuous phase into the flow path 10 from the continuous phase supply path 15, the monoma liquid 20 is supplied toward the flow path 10 from the tip arranged inside the aqueous liquid 25 of the nozzle 12. Nozzle. As a result, the monoma liquid 20 is supplied in a state of being surrounded by the aqueous liquid 25. The monoma liquid 20 is mixed with the aqueous liquid 25 in the flow path 10, thereby forming droplets 21 of the monoma liquid dispersed in the aqueous liquid 25. As a result, the emulsion 30 composed of the droplet 21 as the dispersed phase and the aqueous liquid 25 as the continuous phase is discharged from the outlet of the flow path 10.

By polymerizing the monoma in the obtained emulsion 30, polymer particles having high monodispersity are formed.

(Amphoteric polymer)
The amphoteric polymer forming the coating film is a polymer having a betaine group containing a cationic group and an anionic group. The amphoteric polymer may further have a hydrolyzable silyl group (alkoxysilyl group, etc.). The amphoteric polymer can be, for example, a copolymer having a monoma unit derived from a betaine monoma having a betaine group and a monoma unit having an alkoxysilyl group.

The betaine monoma may be, for example, a monoma having a betaine group selected from the group consisting of a phosphobetaine group, a sulfoxybetaine group, and a carboxybetaine group. These betaine monomas may be used alone or in combination of two or more. Among these betaine monomas, a monoma having a sulfoxybetaine group is preferable because it is excellent in retaining hydrophilicity.

で表わされ、式中、Ｒ^１が、炭素数１〜４のアルキル基を有する（メタ）アクリロイルアミノアルキル基、又は炭素数１〜４のアルキル基を有する（メタ）アクリロイルオキシアルキル基を示し、Ｒ^２及びＲ^３が、それぞれ独立して、水素原子、炭素数１〜４のアルキル基、炭素数１〜４のヒドロキシアルキル基、又は炭素数１〜４のアルキル基を有する（メタ）アクリロイルオキシアルキル基を示し、Ｒ^４は炭素数１〜４のアルキレン基又は炭素数１〜４のオキシアルキレン基を示す、スルホキシベタインモノマが挙げられる。式（Ｉ）で表わされるスルホキシベタインモノマは、両性ポリマの保持性を向上させる観点から好ましい。 The monoma having a sulfoxybetaine group (sulfoxivetaine monoma) is not particularly limited, and examples thereof include a sulfoxybetaine monoma having a (meth) acryloyl group. Suitable sulfoxybetaine monomas include, for example, formula (I):

In the formula, R ¹ indicates a (meth) acryloylaminoalkyl group having an alkyl group having 1 to 4 carbon atoms or a (meth) acryloyloxyalkyl group having an alkyl group having 1 to 4 carbon atoms. , R ² and R ³ each independently have a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms (meth) acryloyl. Examples thereof include ^{sulfoxybetaine monomas, which represent an oxyalkyl group and R 4} represents an alkylene group having 1 to 4 carbon atoms or an oxyalkylene group having 1 to 4 carbon atoms. The sulfoxybetaine monoma represented by the formula (I) is preferable from the viewpoint of improving the retention of the amphoteric polymer.

Expression as the (meth) acryloyl amino alkyl group as R ¹ in (I), for example, (meth) acryloyl aminomethyl group, (meth) acryloyl-aminoethyl group, (meth) acryloyl aminopropyl group and (meth) Acryloyl aminobutyl group can be mentioned. Examples of the (meth) acryloyloxyalkyl group as R ¹ include (meth) acryloyloxymethyl group, (meth) acryloyloxyethyl group, (meth) acryloyloxypropyl group, and (meth) acryloyloxybutyl group. Be done.

^{Examples of the alkyl group having 1 to 4 carbon atoms as R 2} or R ³ in the formula (I) include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the hydroxyalkyl group having 1 to 4 carbon atoms as R ² or R ³ include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group. Examples of the (meth) acryloyloxyalkyl group as R ² or R ³ include (meth) acryloylaminomethyl group, (meth) acryloylaminoethyl group, (meth) acryloylaminopropyl group, and (meth) acryloylaminobutyl. Group is mentioned.

The alkylene group having 1 to 4 carbon atoms as R ⁴ in formula (I), for example, methylene group, ethylene group, propylene group, and butylene group. Examples of the oxyalkylene group having 1 to 4 carbon atoms as R ⁴ include an oxymethylene group, an oxyethylene group, an oxyproprene group, and an oxybutylene group.

で表され、式中、Ｒ^５が炭素数１〜４のアルキレン基又は炭素数１〜４のオキシアルキレン基を示し、Ｒ^６が酸素原子又は−ＮＨ−を示し、Ｒ^７が水素原子又はメチル基を示す、基であることが、親水性、防曇性及び防曇効果の保持性、並びに耐水性が総合的に優れたコーティング膜を形成できる観点から好ましい。 ^{R 1} in the formula (I) is the following formula (Ia):

In the formula, R ⁵ represents an alkylene group having 1 to 4 carbon atoms or an oxyalkylene group having 1 to 4 carbon atoms, R ⁶ represents an oxygen atom or −NH−, and R ⁷ represents a hydrogen atom or methyl. A group showing a group is preferable from the viewpoint of being able to form a coating film having overall excellent hydrophilicity, antifogging property, retention of antifogging effect, and water resistance.

Specific examples of the sulfoxybetaine monoma represented by the formula (I) include N-acryloyloxymethyl-N, N-dimethylammonylmethyl-α-sulfobetaine, N-methacryloyloxymethyl-N, and N-dimethylammoniummethyl-. α-sulfobetaine, N-acryloyloxymethyl-N, N-dimethylammoniumethyl-α-sulfobetaine, N-methacryloyloxymethyl-N, N-dimethylammoniumethyl-α-sulfobetaine, N-acryloyloxymethyl-N , N-Dimethylammoniumpropyl-α-sulfobetaine, N-methacryloyloxymethyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, N-acryloyloxymethyl-N, N-dimethylammonylbutyl-α-sulfobetaine, N-methacryloyloxymethyl-N, N-dimethylammonium butyl-α-sulfobetaine, N-acryloyloxyethyl-N, N-dimethylammonylmethyl-α-sulfobetaine, N-methacryloyloxyethyl-N, N-dimethylammonium Methyl-α-sulfobetaine, N-acryloyloxyethyl-N, N-dimethylammonium ethyl-α-sulfobetaine, N-methacryloyloxyethyl-N, N-dimethylammonium ethyl-α-sulfobetaine, N-acryloyloxyethyl -N, N-dimethylammoniumpropyl-α-sulfobetaine, N-methacryloyloxyethyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, N-acryloyloxyethyl-N, N-dimethylammoniumbutyl-α-sulfo Betain, N-methacryloyloxyethyl-N, N-dimethylammonium butyl-α-sulfobetaine, N-acryloyloxypropyl-N, N-dimethylammonylmethyl-α-sulfobetaine, N-methacryloyloxypropyl-N, N- Dimethylammonylmethyl-α-sulfobetaine, N-acryloyloxypropyl-N, N-dimethylammonium ethyl-α-sulfobetaine, N-methacryloyloxypropyl-N, N-dimethylammonium ethyl-α-sulfobetaine, N-acryloyl Okipropyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, N-methacryloyloxypropyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, N -Acryloyloxypropyl-N, N-dimethylammonium butyl-α-sulfobetaine, N-methacryloyloxypropyl-N, N-dimethylammonium butyl-α-sulfobetaine, N-acryloyloxybutyl-N, N-dimethylammonium methyl -Α-sulfobetaine, N-methacryloyloxybutyl-N, N-dimethylammonium methyl-α-sulfobetaine, N-acryloyloxybutyl-N, N-dimethylammonium ethyl-α-sulfobetaine, N-methacryloyloxybutyl- N, N-dimethylammonium ethyl-α-sulfobetaine, N-acryloyloxybutyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, N-methacryloyloxybutyl-N, N-dimethylammoniumpropyl-α-sulfobetaine , N-Acryloyloxybutyl-N, N-dimethylammonium butyl-α-sulfobetaine, N-methacryloyloxybutyl-N, N-dimethylammonium butyl-α-sulfobetaine, etc. N- (meth) acryloyloxyalkyl-N , N-Dimethylammonium alkyl-α-sulfobetaine;
N-acryloyloxymethoxymethoxy-N, N-dimethylammoniummethyl-α-sulfobetaine, N-methacryloyloxymethoxymethoxy-N, N-dimethylammonylmethyl-α-sulfobetaine, N-acryloyloxymethoxymethoxy-N, N -Dimethylammonium ethyl-α-sulfobetaine, N-methacryloyloxymethoxymethoxy-N, N-dimethylammonium ethyl-α-sulfobetaine, N-acryloyloxymethoxymethoxy-N, N-dimethylammoniumpropyl-α-sulfobetaine, N-methacryloyloxymemethoxymethoxy-N, N-dimethylammoniumpropyl-α-sulfobetaine, N-acryloyloxymethoxymethoxy-N, N-dimethylammoniumbutyl-α-sulfobetaine, N-methacryloyloxymethoxymethoxy-N, N-dimethylammonium butyl-α-sulfobetaine, N-acryloyloxyethoxyethoxy-N, N-dimethylammonylmethyl-α-sulfobetaine, N-methacryloyloxyethoxyethoxy-N, N-dimethylammonylmethyl-α-sulfobetaine , N-acryloyloxyethoxyethoxy-N, N-dimethylammoniumethyl-α-sulfobetaine, N-methacryloyloxyethoxyethoxy-N, N-dimethylammoniumethyl-α-sulfobetaine, N-acryloyloxyethoxyethoxy-N, N-Dimethylammoniumpropyl-α-sulfobetaine, N-methacryloyloxyethoxyethoxy-N, N-dimethylammoniumpropyl-α-sulfobetaine, N-acryloyloxyethoxyethoxy-N, N-dimethylammonylbutyl-α-sulfobetaine , N-Methoxyloyloxyethoxyethoxy-N, N-dimethylammoniumbutyl-α-sulfobetaine, N-acryloyloxypropoxypropoxy-N, N-dimethylammoniummethyl-α-sulfobetaine, N-methacryloyloxypropoxypropoxy-N, N-Dimethylammonium Methyl-α-sulfobetaine, N-acryloyloxypropoxypropoxy-N, N-dimethylammonium ethyl-α-sulfobetaine, N-methacryloyloxypropoxypropoxy-N, N-dimethylammonium ethyl-α-sulfobetaine , N-Acryloyl Okipropoxypro Poxy-N, N-dimethylammonium propyl-α-sulfobetaine, N-methacryloyloxypropoxypropoxy-N, N-dimethylammonium propyl-α-sulfobetaine, N-acryloyloxypropoxypropoxy-N, N-dimethylammonium butyl- α-sulfobetaine, N-methacryloyloxypropoxypropoxy-N, N-dimethylammonium butyl-α-sulfobetaine, N-acryloyloxybutoxybutoxy-N, N-dimethylammoniummethyl-α-sulfobetaine, N-methacryloyloxybutoxy Butoxy-N, N-dimethylammonium methyl-α-sulfobetaine, N-acryloyloxybutoxybutoxy-N, N-dimethylammonium ethyl-α-sulfobetaine, N-methacryloyloxybutoxybutoxy-N, N-dimethylammonium ethyl- α-sulfobetaine, N-acryloyloxybutoxybutoxy-N, N-dimethylammoniumpropyl-α-sulfobetaine, N-methacryloyloxybutoxybutoxy-N, N-dimethylammoniumpropyl-α-sulfobetaine, N-acryloyloxybutoxy N- (meth) acryloyloxyalkoxyannercoxy-N, such as butoxy-N, N-dimethylammonium butyl-α-sulfobetaine, N-methacryloyloxybutoxybutoxy-N, N-dimethylammonium butyl-α-sulfobetaine, etc. N-Dimethylammonium alkyl-α-sulfobetaine;
N, N-diacryloyloxymethyl-N-methylammoniummethyl-α-sulfobetaine, N, N-dimethacryloyloxymethyl-N-methylammonylmethyl-α-sulfobetaine, N, N-diacryloyloxymethyl-N -Methylammonylethyl-α-sulfobetaine, N, N-dimethacryloyloxymethyl-N-methylammonylethyl-α-sulfobetaine, N, N-diacryloyloxymethyl-N-methylammoniumpropyl-α-sulfobetaine, N, N-dimethacryloyloxymethyl-N-methylammoniumpropyl-α-sulfobetaine, N, N-diacryloyloxymethyl-N-methylammoniumbutyl-α-sulfobetaine, N, N-dimethacryloyloxymethyl-N -Methylammonium butyl-α-sulfobetaine, N, N-diacryloyloxyethyl-N-methylammonylmethyl-α-sulfobetaine, N, N-dimethacryloyloxyethyl-N-methylammonium methyl-α-sulfobetaine, N, N-diacryloyloxyethyl-N-methylammonium ethyl-α-sulfobetaine, N, N-dimethacryloyloxyethyl-N-methylammonium ethyl-α-sulfobetaine, N, N-diacryloyloxyethyl-N -Methylammoniumpropyl-α-sulfobetaine, N, N-dimethacryloyloxyethyl-N-methylammoniumpropyl-α-sulfobetaine, N, N-diacryloyloxyethyl-N-methylammoniumbutyl-α-sulfobetaine, N, N-dimethacryloyloxyethyl-N-methylammonium butyl-α-sulfobetaine, N, N-diacryloyloxypropyl-N-methylammonium methyl-α-sulfobetaine, N, N-dimethacryloyloxypropyl-N -Methylammonylmethyl-α-sulfobetaine, N, N-diacryloyloxypropyl-N-methylammonium ethyl-α-sulfobetaine, N, N-dimethacryloyloxypropyl-N-methylammonium ethyl-α-sulfobetaine, N, N-diacryloyl oxypropyl-N-methylammonium propyl-α-sulfobetaine, N, N-dimethacryloyloxypropyl-N-methylammoniumpropyl-α-sulfobetaine, N, N-diacryloyloxypropyl-N -Methylammonium buty Lu-α-sulfobetaine, N, N-dimethacryloyloxypropyl-N-methylammonium butyl-α-sulfobetaine, N, N-diacryloyloxybutyl-N-methylammonium methyl-α-sulfobetaine, N, N -Dimethacryloyloxybutyl-N-methylammonylmethyl-α-sulfobetaine, N, N-diacryloyloxybutyl-N-methylammonium ethyl-α-sulfobetaine, N, N-dimethacryloyloxybutyl-N-methylammonium Ethyl-α-sulfobetaine, N, N-diacryloyloxybutyl-N-methylammoniumpropyl-α-sulfobetaine, N, N-dimethacryloyloxybutyl-N-methylammoniumpropyl-α-sulfobetaine, N, N -N, N-di (meth) acryloyloxyalkyl-such as diacryloyloxybutyl-N-methylammoniumbutyl-α-sulfobetaine, N, N-dimethacryloyloxybutyl-N-methylammoniumbutyl-α-sulfobetaine- N-Methylammonium alkyl-α-sulfobetaine;
N, N, N-triacryloyloxymethylammonium methyl-α-sulfobetaine, N, N, N-trimethacryloyloxymethylammonium methyl-α-sulfobetaine, N, N, N-triacryloyloxymethylammonium ethyl-α -Sulfobetaine, N, N, N-trimethacryloyloxymethylamethylene ethyl-α-sulfobetaine, N, N, N-triacryloxymethylammoniumpropyl-α-sulfobetaine, N, N, N-trimethacryloyloxymethyl Ammoniumpropyl-α-sulfobetaine, N, N, N-triacrylloyloxymethylammonium butyl-α-sulfobetaine, N, N, N-trimethacryloyloxymethylammonium butyl-α-sulfobetaine, N, N, N- Triacryloliloyloxyethylammonylmethyl-α-sulfobetaine, N, N, N-trimethacryloyloxyethylammonylmethyl-α-sulfobetaine, N, N, N-triacryloxyethylammonium ethyl-α-sulfobetaine, N, N, N-Trimethacryloyloxyethylammonium ethyl-α-sulfobetaine, N, N, N-triacryloyloxyethylammoniumpropyl-α-sulfobetaine, N, N, N-tritacryloyloxyethylammoniumpropyl-α- Sulfobetaine, N, N, N-triacryloxyethylammonium butyl-α-sulfobetaine, N, N, N-trimethacryloyloxyethylammonium butyl-α-sulfobetaine, N, N, N-triacryloyloxypropylammonium Methyl-α-sulfobetaine, N, N, N-trimethacryloyloxypropylammonium methyl-α-sulfobetaine, N, N, N-triacryloyloxypropylammonium ethyl-α-sulfobetaine, N, N, N-tri Methylmethacryloyloxyethyl ammonium ethyl-α-sulfobetaine, N, N, N-triacryloyl oxypropylammoniumpropyl-α-sulfobetaine, N, N, N-trimethacryloyloxypropylammoniumpropyl-α-sulfobetaine, N, N , N-Triacryloxypropylammonium butyl-α-sulfobetaine, N, N, N-tri (meth) acrylics such as N, N, N-trimethacryloyloxypropylammonium butyl-α-sulfobetaine. Examples thereof include loyloxyalkylammonium alkyl-α-sulfobetaine. However, sulfoxybetaine monomas are not limited to these exemplified compounds. These sulfoxybetaine monomas may be used alone or in combination of two or more.

で表され、式中、Ｒ^８及びＲ^９が、それぞれ独立して、水素原子又は炭素数１〜４のアルキル基を示し、Ｒ^１０が炭素数が１〜４のアルキル基を有する（メタ）アクリロイルオキシアルキル基を示し、Ｒ^１１が炭素数１〜４のアルキレン基を示す、カルボキシベタインモノマが挙げられる。 Examples of the monoma having a carboxybetaine group (carboxybetaine monoma) include the following formula (II):

In the formula, R ⁸ and R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁰ has an alkyl group having 1 to 4 carbon atoms (meth). Examples thereof include carboxybetaine monomas which show an acryloyloxyalkyl group and R ¹¹ shows an alkylene group having 1 to 4 carbon atoms.

^{Examples of the alkyl group having 1 to 4 carbon atoms as R 8} or R ⁹ in the formula (II) include a methyl group, an ethyl group, a propyl group, and a butyl group.

Expression as the (meth) acryloyloxy alkyl group as R ¹⁰ in (II), for example, (meth) acryloyloxy methyl group, (meth) acryloyloxyethyl group, (meth) acryloyloxy propyl and, (meth) Acryloyloxybutyl group is mentioned.

^{Examples of the alkylene group having 1 to 4 carbon atoms as R 11} in the formula (II) include a methylene group, an ethylene group, a propylene group, and a butylene group.

Specific examples of the carboxybetaine monoma represented by the formula (II) include N-acryloyloxymethyl-N, N-dimethylammonium-α-carboxybetaine, N-methacryloyloxymethyl-N, N-dimethylammonium-α-carboxyl. Betain, N-acryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine, N-methacryloyloxyethyl-N, N-dimethylammonium-α-carboxybetaine, N-acryloyloxypropyl-N, N-dimethylammonium -Α-carboxybetaine, N-methacryloyloxypropyl-N, N-dimethylammonium-α-carboxybetaine, N-acryloyloxybutyl-N, N-dimethylammonium-α-carboxybetaine, N-methacryloyloxybutyl-N, N- (meth) acryloyloxyalkyl-N, N-dimethylammonium-α-carboxybetaine, such as N-dimethylammonium-α-carboxybetaine; N, N-diacryloyloxymethyl-N-methylammonium-α-carboxybetaine , N, N-dimethacryloyloxymethyl-N-methylammonium-α-carboxybetaine, N, N-diacryloyloxyethyl-N-methylammonium-α-carboxybetaine, N, N-dimethacryloyloxyethyl-N- Methylammonium-α-carboxybetaine, N, N-diacryloyloxypropyl-N-methylammonium-α-carboxybetaine, N, N-dimethacryloyloxypropyl-N-methylammonium-α-carboxybetaine, N, N- N, N-di (meth) acryloyloxyalkyl-N-methyl such as diacryloyloxybutyl-N-methylammonium-α-carboxybetaine, N, N-dimethacryloyloxybutyl-N-methylammonium-α-carboxybetaine Ammonium-α-carboxylbetaine; N, N, N-triacryloyloxymethylammonium-α-carboxybetaine, N, N, N-trimethacryloyloxymethylammonium-α-carboxybetaine, N, N, N-triacryloyloxy Ethylammonium-α-carboxybetaine, N, N, N-trimethacryloyloxyethylammonium-α-carboxybetaine, N, N, N- Triacrylloyloxypropylammonium-α-carboxybetaine, N, N, N-trimethacryloyloxypropylammonium-α-carboxybetaine, N, N, N-triacryloxybutylammonium-α-carboxybetaine, N, N, N Examples thereof include N, N, N-tri (meth) acryloyloxyalkylammonium-α-carboxylbetaine such as -trimethacryloyloxybutylammonium-α-carboxybetaine. However, the carboxybetaine monoma is not limited to these exemplified compounds. These carboxybetaine monomas may be used alone or in combination of two or more.

で表され、式中、Ｒ^１２が炭素数が１〜４アルキル基を有する（メタ）アクリロイルオキシアルキル基を示し、Ｒ^１３が炭素数１〜４のアルキレン基を示し、Ｒ^１４、Ｒ^１５及びＲ^１６が、それぞれ独立して、水素原子又は炭素数１〜４のアルキル基を示す、ホスホリルベタインモノマが挙げられる。 Examples of the monoma having a phosphoryl betaine group (phosphoryl betaine monoma) include the following formula (III):

In the formula, R ¹² indicates a (meth) acryloyloxyalkyl group having 1 to 4 alkyl groups, R ¹³ indicates an alkylene group having 1 to 4 carbon atoms, and R ¹⁴ , R ¹⁵ and Examples thereof include phosphoryl betaine monomas in which R ¹⁶ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Expression as the (meth) acryloyloxy alkyl group as R ¹² in (III), for example, (meth) acryloyloxy methyl group, (meth) acryloyloxyethyl group, (meth) acryloyloxy propyl and, (meth) Acryloyloxybutyl group is mentioned.

The alkylene group having 1 to 4 carbon atoms as ^{R 13} in the In the formula (III), the examples thereof include a methylene group, an ethylene group, a propylene group, and butylene group.

^{Examples of the alkyl group having 1 to 4 carbon atoms as R 14} , R ¹⁵ or R ¹⁶ in the formula (III) include a methyl group, an ethyl group, a propyl group and a butyl group.

Specific examples of the phosphorylbetaine monoma represented by the formula (III) include 2-acryloyloxymethylphosphorylcholine, 2-methacryloyloxymethylphosphorylcholine, 2-acryloyloxyethylphosphorylcholine, 2-methacryloyloxyethylphosphorylcholine, and 2-acryloyloxypropylphosphorylcholine. , 2-Methylloyloxypropylphosphorylcholine, 2-acryloyloxybutylphosphorylcholine, and 2-methacryloyloxybutylphosphorylcholine.

The amphoteric polymer may further contain monoma units derived from other monomas other than betaine monomas, as long as the gist of the present invention is not deviated.

Other monomas include, for example, styrene, α-hydroxystyrene, p-hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and the like. Tert-butyl (meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate , (Meta) cetyl acrylate, (meth) ethylcarbitol acrylate, (meth) hydroxyethyl acrylate, (meth) hydroxypropyl acrylate, (meth) hydroxybutyl acrylate, (meth) methoxyethyl acrylate, ( Methoxybutyl acrylate, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N- tert-butyl (meth) acrylamide, N-octyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, (meth) acrylic morpholine, diacetone (meth) acrylamide, styrene, Examples thereof include methyl itaconate, ethyl itaconate, vinyl acetate, vinyl propionate, N-vinylpyrrolidone, and N-vinylcaprolactam. However, other monomas are not limited to these exemplified compounds. The other monomas may be used alone or in combination of two or more.

The amount of monoma units derived from other monomas that may be contained in the amphoteric polymer cannot be unconditionally determined because it differs depending on the type of monoma and the like, but it is appropriate as long as it does not deviate from the gist of the present invention. Can be adjusted.

で表され、式中、Ｒ^１７、Ｒ^１８及びＲ^１９が、それぞれ独立して、炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシ基を示し、Ｒ^１７、Ｒ^１８及びＲ^１９のうちの少なくとも１つの基が炭素数１〜４のアルコキシ基であり、Ｒ^２０が炭素数１〜１２のアルキレン基を示す、化合物、式（Ｖ）：

で表され、式中、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５、Ｒ^２６及びＲ^２７が、それぞれ独立して、炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシ基を示し、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５、Ｒ^２６及びＲ^２７のうちの少なくとも１つの基が炭素数１〜４のアルコキシ基であり、Ｒ^２８及びＲ^２９が、それぞれ独立して、炭素数１〜１２のアルキレン基、又は、炭素数１〜１２のアルキレン基の１個又は２個のメチレン基が−Ｏ−、−Ｃ（Ｏ）Ｏ−、−Ｏ（Ｏ）Ｃ−、−ＮＨ−、−ＣＯ−、アリーレン基、ウレタン基又は１，２−イミダゾリン基に置き換えられた基を示す、アゾビス（トリアルコキシシリル）化合物、２，２’−アゾビス［２−（１−(トリエトキシシリルプロピルカルバモイル)−２−イミダゾリン−２−イル）プロパン］、及び、２，２’−アゾビス［Ｎ−［２−（トリエトキシシリルプロピルカルバモイル）エチル］イソブチルアミド］が挙げられる。アルコキシシリル基含有化合物は、これら例示された化合物のみに限定されるものではない。これらのアルコキシシリル基含有化合物は、それぞれ単独で用いてもよく、２種類以上を併用してもよい。 The amphoteric polymer may have an alkoxysilyl group derived from an alkoxysilyl group-containing compound. Examples of the alkoxysilyl group-containing compound include the formula (IV):

In the formula, R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and are represented by R ¹⁷ , R ¹⁸ and R ^{19 respectively.} Compound, formula (V): wherein at least one of the groups is an alkoxy group having 1 to 4 carbon atoms and R ²⁰ represents an alkylene group having 1 to 12 carbon atoms.

In the formula, R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ , at least one group is an alkoxy group having 1 to 4 carbon atoms, and R ²⁸ and R ²⁹ are independently carbons. One or two methylene groups of the alkylene group having the number 1 to 12 or the alkylene group having the number of carbons 1 to 12 are -O-, -C (O) O-, -O (O) C-, -NH. An azobis (trialkoxysilyl) compound, 2,2'-azobis [2- (1- (triethoxysilyl), showing a group substituted with −, −CO−, arylene group, urethane group or 1,2-imidazolin group. Propylcarbamoyl) -2-imidazolin-2-yl) propane] and 2,2'-azobis [N- [2- (triethoxysilylpropylcarbamoyl) ethyl] isobutylamide] can be mentioned. Alkoxysilyl group-containing compounds are not limited to these exemplified compounds. These alkoxysilyl group-containing compounds may be used alone or in combination of two or more.

Specific examples of the alkoxysilyl group-containing compound represented by the formula (IV) include 2-mercaptomethyltrimethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoproltrimethoxysilane, 2-mercaptobutyltrimethoxysilane, and the like. 2-Mercaptomethyltriethoxysilane, 2-Mercaptoethyltriethoxysilane, 2-Mercaptoproltriethoxysilane, 2-Mercaptobutyltriethoxysilane, 2-Mercaptomethyltripropoxysilane, 2-Mercaptoethyltripropoxysilane, 2- Examples thereof include mercaptoproltripropoxysilane, 2-mercaptobutyltripropoxysilane, 2-mercaptomethyltributoxysilane, 2-mercaptoethyltributoxysilane, 2-mercaptoproltribtoxisilane, and 2-mercaptobutyltributoxysilane. These alkoxysilyl group-containing compounds may be used alone or in combination of two or more.

Specific examples of the alkoxysilyl group-containing compound represented by the formula (V) include 2,2'-azobis [2- (1- (trimethoxysilylpropylcarbamoyl) -2-imidazolin-2-yl) propane], 2 , 2'-azobis [2- (1- (triethoxysilylpropylcarbamoyl) -2-imidazolin-2-yl) propane], 2,2'-azobis [2- (1- (tripropoxysilylpropylcarbamoyl)-) 2-Imidazoline-2-yl) Propane], 2,2'-azobis [N- [2- (trimethoxysilylpropylcarbamoyl) ethyl] isobutyramide], 2,2'-azobis [N- [2- (tri) Ethoxysilylpropylcarbamoyl) ethyl] isobutyramide] and 2,2'-azobis [N- [2- (tripropoxysilylpropylcarbamoyl) ethyl] isobutyramide]. These alkoxysilyl group-containing compounds may be used alone or in combination of two or more.

From the viewpoint of improving the wear resistance of the coating film containing the amphoteric polymer, the alkoxysilyl group-containing compound represented by the formula (V) is preferable.

The weight average molecular weight of the amphoteric polymer is preferably 5,000 or more, 10,000 or more, 15,000 or more, or 20,000 or more from the viewpoint of improving the continuity and repeatability of emulsification. From the viewpoint of enhancing the emulsification and monodispersity of droplets having a large particle size, the weight average molecular weight of the amphoteric polymer is preferably 1,000,000 or less, 100,000 or less, or 50,000 or less. Here, the weight average molecular weight of the amphoteric polymer may be a standard polystyrene-equivalent value that can be measured by, for example, gel permeation chromatography or the like.

The amount of the alkoxysilyl group-containing compound per 100 parts by mass of the monoma subjected to the polymerization is preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more from the viewpoint of improving water resistance and abrasion resistance. It is more preferably 0.3 parts by mass or more, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less from the viewpoint of improving the antifogging property.

When polymerizing the monoma, it is preferable to use a polymerization initiator from the viewpoint of accelerating the polymerization reaction of the monoma component. Examples of the polymerization initiator include azoisobutyronitrile, methyl azoisobutyrate, azobisdimethylvaleronitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate, benzophenone derivative, phosphine oxide derivative, benzoketone derivative, phenylthioether derivative, and azide. Examples thereof include derivatives, diazo derivatives and disulfide derivatives. These polymerization initiators may be used alone or in combination of two or more.

The amount of the polymerization initiator is not particularly limited, but is usually preferably about 0.01 to 5 parts by mass per 100 parts by mass of the total amount of the monoma subjected to the polymerization.

The method for polymerizing the monoma is not particularly limited, and examples thereof include a solution polymerization method. In the case of the solution polymerization method, for example, the monoma can be polymerized by dissolving the monoma in a solvent and adding a polymerization initiator while stirring the obtained solution.

Examples of the solvent include water such as pure water, methyl alcohol, ethyl alcohol, isopropyl alcohol, alcohol such as ethylene glycol and propylene glycol, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether and tetrahydrofuran, benzene, toluene and xylene. Examples thereof include aromatic hydrocarbon compounds such as n-hexane, aliphatic hydrocarbon compounds such as n-hexane, alicyclic hydrocarbon compounds such as cyclohexane, and acetate esters such as methyl acetate and ethyl acetate. These solvents may be used alone or in combination of two or more.

The amount of the solvent is usually preferably adjusted so that the concentration of the monoma in the solution obtained by dissolving the monoma in the solvent is about 10 to 80% by mass.

It is preferable that the polymerization conditions such as the polymerization temperature and the polymerization time when polymerizing the monoma are appropriately adjusted according to the type of the monoma and the amount used thereof, the type of the polymerization initiator and the amount used thereof.

The atmosphere when polymerizing the monoma is preferably an inert gas. Examples of the inert gas include nitrogen gas and argon gas.

The completion of the polymerization reaction and the presence or absence of unreacted monomas in the reaction system can be confirmed by a general analytical method such as gas chromatography.

(Coating film)
The coating film covering the surface of the flow path of the emulsifying device may be composed of only an amphoteric polymer, or may contain a polymer other than the amphoteric polymer within a range not deviating from the gist of the present invention. The content of the amphoteric polymer in the coating film may be 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more based on the mass of the coating film. The coating film can be obtained by molding an amphoteric polymer into a film.

The entire surface of the flow path may be covered with a coating film, but the surface of the flow path may have a portion not covered with the coating film. Of the surface of the flow path, 90 to 100 area% may be covered with a coating film.

The contact angle of water on the surface of the coating film may be 0 to 10 °. The contact angle of water on the surface of the coating film may be 0 to 20 ° after contact with acetone for 24 hours.

The coating film can be formed, for example, by applying a polymer solution containing an amphoteric polymer and a solvent to the surface of the flow path and removing the solvent from the coating film. Examples of the solvent contained in the polymer solution include water such as pure water, alcohol such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol and propylene glycol, ketones such as acetone and methyl ethyl ketone, and ethers such as diethyl ether and tetrahydrofuran. Examples thereof include aromatic hydrocarbon compounds such as benzene, toluene and xylene, aliphatic hydrocarbon compounds such as n-hexane, alicyclic hydrocarbon compounds such as cyclohexane, and acetate esters such as methyl acetate and ethyl acetate. The solvent is not limited to these examples alone. These solvents may be used alone or in combination of two or more.

The amount of the solvent is not particularly limited, but it is usually preferable to adjust the concentration of the amphoteric polymer in the coating liquid to be about 10 to 80% by mass.

The method of applying the polymer solution containing the amphoteric polymer to the surface of the flow path is not particularly limited, and examples thereof include a roll coating method, a gravure coating method, a spin coating method, a doctor blade method, a dipping method, and a brush coating method. ..

The atmosphere when the polymer solution containing the amphoteric polymer is applied to the surface of the flow path may be usually the atmosphere. The temperature at which the polymer solution is applied to the surface of the flow path may be usually room temperature or heating.

When removing the solvent from the coating film, the formed coating film may be heated, if necessary. The heating temperature may be any temperature as long as the solvent contained in the formed coating film evaporates, and may be, for example, 30 to 300 ° C., 40 to 250 ° C., 50 to 230 ° C., or 50 to 150 ° C. May be good. The heating time varies depending on the heating temperature and the like and cannot be unconditionally determined, but is usually about 10 minutes to 5 hours. Heating can be performed in one step or in multiple steps of two or more steps. As an example, for example, a method of drying at a temperature of 30 to 80 ° C. for 10 minutes to 2 hours and then heating at a temperature of 100 to 250 ° C. for another 10 minutes to 2 hours can be mentioned. The atmosphere for heating the coating film may be the atmosphere or the atmosphere of an inert gas such as nitrogen gas. The atmosphere for heating the coating film may be atmospheric pressure or reduced pressure.

The thickness of the coating film after drying is not particularly limited, but is preferably 1 to 500 μm, more preferably 2 to 300 μm, still more preferably 2 to 300 μm, from the viewpoint of increasing the strength of the coating film and imparting flexibility to the coating film. It is 3 to 200 μm, and even more preferably 5 to 150 μm.

(Polymer particles)
By polymerizing the monoma in the emulsifying liquid formed by the emulsifying device, spherical polymer particles containing the polymer of the monoma are formed. The monoma is not particularly limited, but may include, for example, a styrene-based vinyl monoma. Examples of the monoma include the following polyfunctional monomas, monofunctional monomas and the like.

The polyfunctional monoma may be, for example, a crosslinkable monoma having an aromatic group and two or more vinyl groups bonded to the aromatic group. Specific examples thereof include divinylbenzene, divinylbiphenyl, divinylnaphthalene, and divinylphenanthrene. These polyfunctional monomas can be used alone or in combination of two or more. Among the above, it is preferable to use divinylbenzene because it is excellent in durability, acid resistance and alkali resistance.

When the monoma contains divinylbenzene, the content thereof is preferably 50% by mass or more, 60% by mass or more, or 70% by mass or more based on the total mass of the monoma. By containing a large amount of divinylbenzene, it tends to be more excellent in durability, acid resistance and alkali resistance.

Examples of monofunctional monomas include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, 2,4-. Diethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, pt-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decyl Examples thereof include styrene such as styrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene and derivatives thereof. These monofunctional monomas can be used alone or in combination of two or more. Of these, styrene is preferably used from the viewpoint of excellent acid resistance and alkali resistance. Styrene derivatives having functional groups such as carboxy group, amino group, hydroxyl group and aldehyde group can also be used.

The monoma solution may contain a polymerization initiator, if necessary. Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, benzoyl orthochloro peroxide, benzoyl orthomethoxy peroxide, 3,5,5-trimethylhexanoyl peroxide, and tert-butylperoxy-2-ethylhexano. Organic peroxides such as ate, di-tert-butyl peroxide; 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile, 2,2'-azobis (2,4-azobis) Examples thereof include azo compounds such as dimethylvaleronitrile). The polymerization initiator can be used in the range of 0.1 to 7.0 parts by mass with respect to 100 parts by mass of the monoma.

The polymer particles of the present embodiment may be porous particles. Porous particles are particles formed from a monoma solution containing a porosifying agent, and are synthesized by ordinary suspension polymerization, emulsion polymerization, or the like.

Examples of the porosifying agent include aliphatic or aromatic hydrocarbons, esters, ketones, ethers, alcohols, etc., which are organic solvents that promote phase separation during polymerization and promote porosification of particles. Be done. Specific examples thereof include toluene, xylene, cyclohexane, octane, butyl acetate, dibutyl phthalate, methyl ethyl ketone, dibutyl ether, 1-hexanol, 2-octanol, decanol, lauryl alcohol and cyclohexanol. These porosifying agents can be used alone or in combination of two or more.

The amount of the porosifying agent may be 0 to 200% by mass with respect to the total mass of the monoma. The porosity of the porous particles can be controlled by the amount of the porosity agent. Furthermore, the size and shape of the pores of the porous particles can be controlled by the type of the porosifying agent.

The pore volume of the porous particles is preferably 30% by volume or more and 70% by volume or less, and more preferably 40% by volume or more and 70% by volume or less based on the total volume of the porous particles. The porous particles preferably have pores having an average pore diameter of 0.1 μm or more and less than 0.6 μm, that is, macropores (macropores). The average pore size of the porous particles is more preferably 0.2 μm or more and less than 0.6 μm. When the average pore diameter is 0.1 μm or more, substances tend to enter the pores easily, and when the average pore diameter is less than 0.6 μm, the specific surface area becomes sufficient. These can be adjusted by the above-mentioned porosifying agent.

The specific surface area of the porous particles is preferably 30 m2 / g or more. From the viewpoint of higher practicality, the specific surface area is more preferably 35 m2 / g or more, and further preferably 40 m2 / g or more.

Water used as a continuous phase of the emulsion can also be used as a porosifying agent. When water is used as a porosifying agent, it can be made porous by dissolving an oil-soluble surfactant in a monoma and absorbing water.

Examples of the oil-soluble surfactant used as the porosifying agent include sorbitan monoesters of branched C16 to C24 fatty acids, chain unsaturated C16 to C22 fatty acids or chain saturated C12 to C14 fatty acids, for example, sorbitan monolaurate. Solbitan monoester derived from sorbitan monooleate, sorbitan monomillistate or coconut fatty acid; diglycerol monoester of branched C16-C24 fatty acid, chain unsaturated C16-C22 fatty acid or chain saturated C12-C14 fatty acid, eg Diglycerol monooleate (eg, diglycerol monoester of C18: 1 (18 carbons, 1 double bond) fatty acid), diglycerol monomillistate, diglycerol monoisostearate or diglycerol of coconut fatty acid Monoesters; diglycerol monofatty acids of branched C16-C24 alcohols (eg, gelve alcohols), chain unsaturated C16-C22 alcohols or chain saturated C12-C14 alcohols (eg palm fatty alcohols); and mixtures thereof. Can be mentioned

Of these, sorbitan monolaurate (eg, SPAN® 20, preferably with a purity of more than about 40%, more preferably with a purity of more than about 50%, even more preferably with a purity of more than about 70%. Monolaurate); sorbitan monooleate (eg, SPAN® 80, preferably with a purity of greater than about 40%, more preferably greater than about 50%, even more preferably greater than about 70%. Sorbitan monooleate); diglyceride monooleate (preferably more than about 40% pure, more preferably more than about 50% pure, even more preferably more than about 70% pure diglycerol monooleate); diglycerol Monoisostearate (preferably diglycerol monoisostearate with a purity greater than about 40%, more preferably greater than about 50%, even more preferably greater than about 70% purity); diglyceride monomillistate (preferably greater than about 70%). Sorbitan monomillistate with a purity greater than about 40%, more preferably greater than about 50%, even more preferably greater than about 70%; diglyceride cocoyl (eg, lauryl group, myristyl group, etc.) ether; A mixture of these is preferred.

These oil-soluble surfactants are preferably used in the range of 5 to 80% by mass with respect to the total mass of the monoma. When the content of the oil-soluble surfactant is 5% by mass or more, the stability of the water droplet is sufficient, so that a large single pore is easily formed. Further, when the content of the oil-soluble surfactant is 80% by mass or less, the polymer particles are more likely to retain their shape after polymerization.

The aqueous solution as the continuous phase of the emulsion comprises water and an aqueous medium such as a mixed solvent of water and a water-soluble solvent (eg, lower alcohol). The aqueous liquid may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic and zwitterionic surfactants can be used.

Examples of the anionic surfactant include fatty acid oils such as sodium oleate and potassium castor oil, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, and alkylnaphthalene sulfone. Dialkyl sulfosuccinates such as acid salts, alkane sulfonates, sodium dioctyl sulfosuccinate, alkernyl succinate (dipotassium salt), alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl phenyl ether sulfate Examples thereof include salts, polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate, and polyoxyethylene alkyl sulfates.

Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.

Examples of nonionic surfactants include hydrocarbon-based nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines, and amides. Examples thereof include polyethylene oxide adducts of silicon, polyether-modified silicon nonionic surfactants such as polypropylene oxide adducts, and fluorine nonionic surfactants such as perfluoroalkyl glycols.

Examples of the zwitterionic surfactant include hydrocarbon surfactants such as lauryldimethylamine oxide, phosphoric acid ester-based surfactants, and phosphite ester-based surfactants.

As the surfactant, one type may be used alone or two or more types may be used in combination. Among the above-mentioned surfactants, anionic surfactants are preferable from the viewpoint of dispersion stability during monoma polymerization.

The polymerization temperature can be appropriately selected depending on the type of the monoma and the polymerization initiator. The polymerization temperature is preferably 25 to 110 ° C, more preferably 50 to 100 ° C.
In the synthesis of polymer particles, a polymer dispersion stabilizer may be used in order to improve the dispersion stability of the particles.

The emulsion may contain a polymer dispersion stabilizer. Examples of the polymer dispersion stabilizer include polyvinyl alcohol, polycarboxylic acid, celluloses (hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, etc.), polyvinylpyrrolidone, and an inorganic water-soluble polymer compound such as sodium tripolyphosphate is also used in combination. can do. Of these, polyvinyl alcohol or polyvinylpyrrolidone is preferable. The amount of the polymer dispersion stabilizer is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the monoma.

In order to prevent the monoma from polymerizing alone, a water-soluble polymerization inhibitor such as nitrites, sulfites, hydroquinones, ascorbic acids, water-soluble B vitamins, citric acid, and polyphenols may be used.

The average particle size of the polymer particles and the droplets before polymerization is preferably 300 μm or less, 150 μm or less, or 100 μm or less. The average particle size of the polymer particles is preferably 1 μm or more, 10 μm or more, 30 μm or more, or 50 μm or more from the viewpoint of improving the liquid permeability when the polymer particles are used as a column packing material. The particle size here means the maximum width of the particles.

The coefficient of variation (CV) of the particle size of the polymer particles is preferably 15% or less, 3 to 15%, 5 to 15%, or 5 to 10% from the viewpoint of improving the liquid permeability.

The average particle size and the coefficient of variation of the particle size of the droplets of the monoma solution before polymerization may be in the same range as described above.

C.I. V. The (coefficient of variation) can be obtained by the following measurement method.
1) The particles are dispersed in water (including a dispersant such as a surfactant) using an ultrasonic disperser to prepare a dispersion liquid containing 1% by mass of polymer particles.
2) Using a particle size distribution meter (Sysmex Flow, manufactured by Sysmex Corporation), C.I. V. Measure (coefficient of variation).

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Example 1)
(Synthesis of amphoteric polymers)
N-acryloylaminopropyl-N, N-dimethylammoniumpropyl-α-sulfoxibetaine (manufactured by Sigma-Aldrich Japan GK, product number: 473160-5G) in a 500 mL corben equipped with a nitrogen gas introduction tube, condenser and stirrer. ) 49 g, 0.35 g of 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: KBM-803) and 115.15 g of pure water were added as a silane coupling agent. After degassing by depressurizing the inside of the corben, nitrogen gas was introduced into the corben to return to normal pressure, and the oxygen gas in the corben was eliminated as much as possible.

Next, the contents of Kolben were heated to 65 ° C. by the oil bath provided in Kolben. Then, 0.99 g of 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] (manufactured by Wako Pure Chemical Industries, Ltd., product number: VA-086, molecular weight: 288.35) was added to corben. Was added, and the contents of Kolben were aged for 4 hours while maintaining the temperature at 70 ° C. Then, 0.49 g of 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] is further added to the corben, and the content of the corben is aged for 4 hours while maintaining the temperature at 70 ° C. As a result, a polymer solution having a concentration of 5% by mass containing an amphoteric polymer having a sulfoxybetaine group and an alkoxysilyl group was obtained.

The obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 329.0 g of water to obtain a transparent polymer solution. The weight average molecular weight (standard polystyrene conversion value) of the amphoteric polymer contained in the polymer solution was measured by gel permeation chromatography (manufactured by Tosoh Corporation, product number: HLC-8320 GPC) and found to be 3,2000. ..

(Coating of emulsifying device with amphoteric polymer)
An emulsifying device having a microchannel having a width of 130 μm (manufactured by Synthetic Fiber Nozzle Mfg. Co., Ltd.) was immersed in the polymer solution for 5 minutes, and the removed emulsifying device was naturally dried. Then, the emulsifying device was aged at 80 ° C. for 1 hour, and further washed with pure water to form a coating film of an amphoteric polymer covering the microchannel of the emulsifying device.

(Contact angle measurement)
The contact angle of water in the atmosphere on the surface of the formed coating film was measured. Furthermore, the emulsifying device was immersed in acetone, and then the contact angle of water in the air of the coating film was measured. The contact angle was calculated by the θ / 2 method in image analysis using a contact angle measuring device after water was dropped on the surface of the coating film. When the contact angle was too small to measure, it was set as "-".

(Emulsification test)
Using an emulsifying device having an amphoteric polymer coating film, it is dissolved in an aqueous solution of sodium lauryl sulfate as a continuous phase at a concentration of 50 ppm, divinylbenzene as a dispersed phase (content 96%), and a concentration of 0.05% by mass. An emulsified solution consisting of a monoma solution containing benzoyl peroxide (25% water content) was prepared. While supplying a continuous phase to the microchannel of the emulsifying device at a flow rate of 70 mL / h, a monoma solution as a dispersed phase is injected into the microchannel at a flow rate of 30 mL / h from a nozzle provided near the inlet of the flow path. Emulsification was performed in the passage, and the emulsified liquid was recovered from the outlet of the microchannel. 200 droplets of the monoma solution dispersed in the obtained emulsion were observed with an optical microscope, and the average particle size and the coefficient of variation (CV) of the particle size were calculated.

Continuity evaluation With the emulsifying device, the time during which the emulsion can be formed uniformly and stably was measured while maintaining the coefficient of variation of the particle size of 15% or less. The measured time of 3 hours or more was determined as "A", and the measured time of less than 3 hours was determined as "C".

Repeatability evaluation The inside of the flow path of the emulsifying device is not washed, and the same emulsion is repeatedly formed. In the emulsifying device, the emulsion is uniformly and stably produced while maintaining the coefficient of variation of the particle size of 15% or less. It was evaluated how many times it could be formed repeatedly. It was judged that the number of repetitions in which a uniform and stable emulsion could be formed was 10 times or more as "A" and less than 10 times as "C".

(Polymerization and purification)
Nitrogen bubbling was performed in the recovered emulsion for 1 hour. Then, the temperature of the emulsion was raised to 80 ° C., and the temperature was maintained for 6 hours to allow the polymerization reaction of divinylbenzene to proceed. The produced polymer particles were washed with ultrapure water and acetone, and then dispersed in acetone. The obtained dispersion was filtered through a sieve of 200 μm mesh and a sieve of 60 μm mesh, and the polymer particles remaining on the sieve of 60 μm mesh were dried under reduced pressure to obtain a powder of the polymer particles.

(Example 2)
In the synthesis of amphoteric polyma, 2-methacryloyloxyethyl phosphorylcholine (manufactured by Tokyo Kasei Kogyo Co., Ltd., product number: M2005) was used instead of N-acryloylaminopropyl-N, N-dimethylammoniumpropyl-α-sulfoxibetaine. An emulsifying device having a microchannel covered with a coating film was prepared in the same manner as in Example 1 except that an amphoteric polymer having a phosphoryl betaine group and an alkoxysilyl group was obtained. Using this emulsification device, the continuity and repeatability of emulsification were evaluated in the same manner as in Example 1, and a polymerization reaction was further carried out.

(Example 3)
In the synthesis of amphoteric polyma, instead of N-acryloylaminopropyl-N, N-dimethylammoniumpropyl-α-sulfoxibetaine, N-acryloylaminoethyl-N, N-dimethylammoniummethyl-α-carboxybetaine (Osaka Organic) Micro-coated with a coating film in the same manner as in Example 1 except that an amphoteric polymer having a carboxybetaine group and an alkoxysilyl group was obtained using (Chemical Industry Co., Ltd., product number: CMBAm). An emulsifying device having a flow path was prepared. Using this emulsification device, the continuity and repeatability of emulsification were evaluated in the same manner as in Example 1, and a polymerization reaction was further carried out.

(Example 4)
(Synthesis of amphoteric polymers)
N-acryloylaminopropyl-N, N-dimethylammoniumpropyl-α-sulfoxybetaine 49 g, 3-mercaptopropyltri as a silane coupling agent, in a 500 mL volume of corben equipped with a nitrogen gas introduction tube, a condenser and a stirrer. 0.35 g of methoxysilane and 197.40 g of pure water were added. After degassing by depressurizing the inside of the corben, nitrogen gas was introduced into the corben to return to normal pressure, and the oxygen gas in the corben was eliminated as much as possible.

Next, the contents of Kolben were heated to 65 ° C. by the oil bath provided in Kolben. Then, 2.47 g of 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] was added to corben and aged for 4 hours while maintaining the temperature of the contents of corben at 70 ° C. .. Then, 0.49 g of 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] is further added to the corben, and the content of the corben is aged for 4 hours while maintaining the temperature at 70 ° C. As a result, a polymer solution having a concentration of 5% by mass containing an amphoteric polymer having a sulfoxybetaine group and an alkoxysilyl group was obtained.

The obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 246.7 g of water to obtain a transparent polymer solution. The weight average molecular weight (standard polystyrene conversion value) of the amphoteric polymer contained in the polymer solution was measured by gel permeation chromatography and found to be 1,4000.

An emulsifying device having a microchannel covered with a coating film was prepared in the same manner except that the obtained amphoteric polymer was used. Using this emulsification device, the continuity and repeatability of emulsification were evaluated in the same manner as in Example 1, and a polymerization reaction was further carried out.

(Example 5)
N-acryloylaminopropyl-N, N-dimethylammoniumpropyl-α-sulfoxybetaine 49 g, 3-mercaptopropyltrimethoxy as a silane coupling agent in 500 mL of corben equipped with a nitrogen gas introduction tube, condenser and stirrer. 0.35 g of silane and 49.35 g of pure water were added. After degassing by depressurizing the inside of the corben, nitrogen gas was introduced into the corben to return to normal pressure, and the oxygen gas in the corben was eliminated as much as possible.

Next, the contents of Kolben were heated to 65 ° C. by the oil bath provided in Kolben. Then, 0.10 g of 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] was added to corben and aged for 4 hours while maintaining the temperature of the contents of corben at 70 ° C. It was. Then, 0.49 g of 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] is further added to the corben, and the content of the corben is aged for 4 hours while maintaining the temperature at 70 ° C. As a result, a polymer solution having a concentration of 5% by mass containing an amphoteric polymer having a sulfoxybetaine group and an alkoxysilyl group was obtained.

The polymer solution was cooled to 30 ° C. in a water bath and diluted with 394.8 g of water to obtain a transparent polymer solution. The weight average molecular weight (standard polystyrene conversion value) of the amphoteric polymer contained in the polymer solution was measured by gel permeation chromatography and found to be 10,5000.

An emulsifying device having a microchannel covered with a coating film was prepared in the same manner as in Example 1 except that the obtained amphoteric polymer was used. Using this emulsification device, the continuity and repeatability of emulsification were evaluated in the same manner as in Example 1, and a polymerization reaction was further carried out.

(Comparative Example 1)
An emulsification device having a microchannel made of stainless steel (SUS) was used without forming a coating film of an amphoteric polymer, and the continuity and repeatability of emulsification were evaluated in the same manner as in Example 1.

(Comparative Example 2)
The continuity and repeatability of emulsification were evaluated in the same manner as in Example 1 using an emulsification device having a glass microchannel without forming a coating film of an amphoteric polymer.

(Comparative Example 3)
Except for the use of dimethylaminoethyl acrylate methyl chloride quaternary salt (manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: DMAMC) instead of N-acryloylaminopropyl-N, N-dimethylammoniumpropyl-α-sulfoxibetaine. Obtained a cationic polymer having an ammonium group and an alkoxysilyl group in the same manner as in Example 1.

An emulsifying device having a microchannel covered with a coating film was prepared in the same manner as in Example 1 except that the obtained cationic polymer was used. Using this emulsification device, the continuity and repeatability of emulsification were evaluated in the same manner as in Example 1, and a polymerization reaction was further carried out.

(Comparative Example 4)
2-acrylamide-2-methylpropansulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd., product number: 017-15722) is used instead of N-acryloylaminopropyl-N, N-dimethylammoniumpropyl-α-sulfoxibetaine. An anionic polymer having a sulfo group and an alkoxysilyl group at a concentration of 5% by mass was obtained in the same manner as in Example 1 except for the above.

An emulsifying device having a microchannel covered with a coating film was prepared in the same manner as in Example 1 except that the obtained polymer was used. Using this emulsification device, the continuity and repeatability of emulsification were evaluated in the same manner as in Example 1, and a polymerization reaction was further carried out.

(Comparative Example 5)
Conducted except that methoxytriethylene glycol acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V # MTG) was used instead of N-acryloylaminopropyl-N and N-dimethylammoniumpropyl-α-sulfoxivetain. In the same manner as in Example 1, a nonionic polymer having an oxyethylene group and an alkoxysilyl group was obtained.

An emulsifying device having a microchannel covered with a coating film was prepared in the same manner as in Example 1 except that the obtained polymer was used. Using this emulsification device, the continuity and repeatability of emulsification were evaluated in the same manner as in Example 1, and a polymerization reaction was further carried out.

As shown in Table 1, according to the example using the flow path covered with the coating film of the amphoteric polymer, it was confirmed that the polymer particles were continuously and repeatedly obtained with high monodispersity.

1 ... emulsifying device, 10 ... flow path, 10S ... flow path surface, 12 ... nozzle, 13 ... first member, 14 ... second member, 15 ... continuous phase supply path, 20 ... monoma liquid, 21 ... monoma Liquid droplets, 25 ... aqueous liquid, 30 ... emulsion.

Claims (12)

In the flow path of the emulsifying device, a monoma liquid containing monoma is mixed with an aqueous liquid containing water to form an emulsified liquid containing droplets of the monoma liquid as a dispersed phase and the aqueous liquid as a continuous phase. And the process of making
A step of polymerizing the monoma in the emulsion to form polymer particles containing the polymer of the monoma, and a step of forming the polymer particles.
Including
The surface of the flow path is covered with a coating film containing an amphoteric polymer.
A method of producing polymer particles. The method according to claim 1, wherein the amphoteric polymer has at least one betaine group selected from the group consisting of a phosphobetaine group, a sulfoxybetaine group, and a carboxybetaine group. The method according to claim 1 or 2, wherein the monoma liquid is dispersed in the aqueous liquid by supplying the monoma liquid inside the aqueous liquid while pouring the aqueous liquid into the flow path. The method according to any one of claims 1 to 3, wherein the contact angle of water on the surface of the coating film is 0 to 10 °. The method according to any one of claims 1 to 4, wherein the monoma comprises a crosslinkable monoma having an aromatic group and two or more vinyl groups bonded to the aromatic group. The method according to any one of claims 1 to 5, wherein the surface of the flow path is formed of metal or glass. The method according to any one of claims 1 to 6, wherein the contact angle of water on the surface of the coating film is 0 to 20 ° after contact with acetone for 24 hours. The method according to any one of claims 1 to 7, wherein the amphoteric polymer has a hydrolyzable silyl group. The method according to any one of claims 1 to 8, wherein the average particle size of the droplets of the monoma solution is 1 to 300 μm, and the average particle size of the polymer particles is 1 to 300 μm. The method according to any one of claims 1 to 9, wherein the coefficient of variation of the particle size of the droplets of the monoma liquid is 15% or less, and the coefficient of variation of the particle size of the polymer particles is 15% or less. The method according to any one of claims 1 to 10, wherein the weight average molecular weight of the amphoteric polymer is 5,000 to 1,000,000. The method according to any one of claims 1 to 11, wherein the polymer particles are porous particles.

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